The thermal stability and crystalline phases precipitated from the as-cast rods of the Cu50Zr50-based alloys with addition of Al or simultaneous addition of Al/Ti or Al/Ag elements were investigated using DSC, DTA and XRD. The value of Tx, Trg and γ as a function of alloy composition shows a same trend, in which the Cu46Zr46Al8 alloy exhibits the largest value of Tx, Trg and γ. However, this trend is different from the variation of the dc with alloy composition, in which the Cu42Zr42Al8Ag8 alloy has the largest dc for glass formation. Trg′ based on Tg/Tm has a good correlation with the critical diameter for glass formation in this alloy system. It was found that the alloy with higher GFA has more complex precipitated crystalline phases from the as-cast rod with a diameter larger than the critical diameter for glass formation.